CN106463784B

CN106463784B - Nickel-zinc cell

Info

Publication number: CN106463784B
Application number: CN201580002787.8A
Authority: CN
Inventors: 林洋志; 山田直仁; 鬼头贤信
Original assignee: NGK Insulators Ltd
Current assignee: NGK Insulators Ltd
Priority date: 2014-07-09
Filing date: 2015-05-21
Publication date: 2019-03-08
Anticipated expiration: 2035-05-21
Also published as: CN106463783A; WO2016006331A1; JPWO2016006330A1; JPWO2016006331A1; CN106463784A; WO2016006330A1; EP3076476A1; EP3076476A4; EP3076476B1; JP2016129156A; JP6189469B2; JP5917780B1; EP3076477B1; US20160294018A1; US10381689B2; US10128542B2; CN106463783B; US20160276714A1; JP5914775B1; EP3076477A1

Abstract

The present invention provides a kind of nickel-zinc cell of high reliability, and it uses with hydroxide ion conductibility but without the partition of water penetration.Nickel-zinc cell of the invention includes: the anode containing nickel hydroxide and/or hydroxy nickel oxide, dipping anode and the anode electrolyte containing alkali metal hydroxide, cathode containing zinc and/or zinc oxide, impregnate cathode and the electrolyte liquid containing alkali metal hydroxide, accommodate anode, anode electrolyte, the closed container of cathode and electrolyte liquid, the anode chamber zoning for being arranged to the cathode chamber that will accommodate anode and anode electrolyte in closed container and accommodating cathode and electrolyte liquid is opened, with hydroxide ion conductibility but without the partition of water penetration, the porous substrate of the positive side surface of partition is set.

Description

Nickel-zinc cell

Technical field

The present invention relates to a kind of nickel-zinc cells.

Background technique

It is not yet practical although all developing all the time and studying Ni-MH secondary battery.The reason is that existing as follows Problem: the zinc that cathode is constituted when charging generates the ingotism for being referred to as dendrite, which punctures partition, occurs with anode short Road.On the other hand, nickel-cadmium cell and nickel-metal hydride battery have been commercialized.However, Ni-MH secondary battery has high theoretical capacity Density, it is about 5 times higher than ni-Cd secondary cell, it is 2.5 times higher than nickel-hydrogen secondary cell, it is 1.3 times higher than lithium ion battery, also, have There is the relatively low such advantage of cost of material.Therefore, for Ni-MH secondary battery, being strongly desired to develop prevents zinc dendrite from causing Short circuit technology.

It is short-circuit caused by zinc dendrite in order to prevent such as in patent document 1 (International Publication No. 2013/118561) Purpose is proposed the partition formed by the conductive inorganic solid electrolyte body of hydroxide ion setting in anode and cathode Between Ni-MH secondary battery.Disclose in the publication: the relative density of the inorganic solid electrolyte body is 90% or more, can By basic composition is general formula: M²⁺ _1-xM³⁺ _x(OH)₂A^n- _x/n·mH₂O (in formula, M²⁺For the divalent cation of at least one or more, M³⁺ For the trivalent cation of at least one or more, A^n-For the anion of n valence, the integer that n is 1 or more, x is 0.1~0.4) stratiform it is double Hydroxide is formed.

In addition, it is also known that in the hermetic type nickel-zinc cell for the oxygen that cathode absorbs and cycle charging latter stage generates.Such as It is disclosed in patent document 2 (Japanese Unexamined Patent Publication 5-303978 bulletin) and has polar plate group and configuration around the polar plate group The hermetic type nickel-zinc cell of guarantor's liquid layer, the polar plate group has positive plate, negative plate, partition and retainer, and discloses guarantor's liquid Layer is the layer containing electrolyte in 0.5~50mm of length, 5~100 μm of diameter of cellulose fibre.In the patent document 2, Use partition obtained by handling polypropylene porous film with surfactant.At patent document 3 (Japanese Unexamined Patent Publication 6-96795 Bulletin) in, it discloses a kind of hermetic type nickel-zinc cell, configures the pad-face of poling group and battery groove bottom is opposite and electrolyte Volume be more than the 98% of the gross space volume of pole group and 110% hereinafter, microporosity film and cellophane film can be used as partition.

It is also known that being easy to reach the technology of cathode via partition by the oxygen that anode generates in overcharge.Such as in patent It discloses in document 4 (Japanese Unexamined Patent Publication 5-36394 bulletin) by least on surface, there are the hydrophobic resins of hydrophilic fibre The separator for alkaline cell that porous body film is formed.

Existing technical literature

Patent document

Patent document 1: International Publication No. 2013/118561

Patent document 2: Japanese Unexamined Patent Publication 5-303978 bulletin

Patent document 3: Japanese Unexamined Patent Publication 6-96795 bulletin

Patent document 4: Japanese Unexamined Patent Publication 5-36394 bulletin

Summary of the invention

Nowadays the inventors of the present invention have found using having hydroxide ion conductibility but the partition without water penetration can mention For the nickel-zinc cell of high reliablity.

Therefore, the purpose of the present invention is to provide a kind of nickel-zinc cell of high reliablity, it uses with hydroxide Ionic conductivity but the partition for not having water penetration.

A scheme according to the present invention, provides a kind of nickel-zinc cell, it includes:

Anode, the anode contain nickel hydroxide and/or hydroxy nickel oxide,

Anode electrolyte, the anode electrolyte contain alkali metal hydroxide, impregnate the anode,

Cathode, the cathode contain zinc and/or zinc oxide,

Electrolyte liquid, the electrolyte liquid contain alkali metal hydroxide, impregnate the cathode,

Closed container, the closed container accommodate the anode, the anode electrolyte, the cathode and the negative electricity Liquid is solved,

Partition, the partition have hydroxide ion conductibility but do not have water penetration, set in the closed container The cathode chamber of the anode and the anode electrolyte will be accommodated and accommodates the negative of the cathode and the electrolyte liquid by being set to Pole room zoning is opened,

The positive side surface of the partition is arranged in porous substrate, the porous substrate.

Detailed description of the invention

Fig. 1 is the schematic diagram for schematically showing an example of nickel-zinc cell of the invention, indicates electric discharge last current state.

Fig. 2 is the figure for indicating the fully charged state of nickel-zinc cell shown in FIG. 1.

Fig. 3 is the schematic diagram for schematically showing an example of laminated type nickel-zinc cell arranged side by side of the invention, indicates electric discharge end State.

Fig. 4 is the diagrammatic cross-sectional view for indicating to be accompanied with a scheme of partition for porous substrate.

Fig. 5 is the diagrammatic cross-sectional view for indicating to be accompanied with another scheme of partition of porous substrate.

Fig. 6 is the schematic diagram for indicating layered double-hydroxide (LDH) platy particles.

Fig. 7 is the SEM image on the surface of the oxidation aluminum porous substrate made in example 1.

Fig. 8 is the XRD spectrum that the crystalline phase in example 1 for sample obtains.

Fig. 9 is the SEM image for indicating the surface micro-structure for the film sample observed in example 1.

Figure 10 is the SEM image of the grinding section micro-structure for the composite sample observed in example 1.

Figure 11 A is the exploded perspective view that compactness used in example 1 differentiates measurement system.

Figure 11 B is the diagrammatic cross-sectional view that compactness used in example 1 differentiates measurement system.

Figure 12 is the diagrammatic cross-sectional view for schematically showing the state that the growth of zinc dendrite is prevented by partition.It should be noted that being Facilitate diagram, is omitted anode electrolyte 14 and electrolyte liquid 18.

Specific embodiment

Nickel-zinc cell

An example of nickel-zinc cell of the invention is schematically shown in Fig. 1.Nickel-zinc cell shown in FIG. 1 is before being charged A-stage, be equivalent to electric discharge last current state.But nickel-zinc cell of the invention can certainly be constituted with fully charged state. As shown in Figure 1, nickel-zinc cell 10 of the invention has positive 12, anode electrolyte 14, cathode 16, cathode in closed container 22 Electrolyte 18, partition 20 and porous substrate 28.Anode 12 includes nickel hydroxide and/or hydroxy nickel oxide.Anode electrolyte 14 wraps Alkali metal containing hydroxide, dipping anode 12.Cathode 16 includes zinc and/or zinc oxide.Electrolyte liquid 18 includes alkali metal hydrogen Oxide impregnates cathode 16.Closed container 22 accommodates anode 12, anode electrolyte 14, cathode 16 and electrolyte liquid 18.Anode 12 and anode electrolyte 14 might not be to be separated, be also configured to anode 12 and the anode that mixes of anode electrolyte 14 Mixture.Similarly, cathode 16 and electrolyte liquid 18 might not be to be separated, are also configured to cathode 16 and electrolyte liquid 18 cathode agents mixed.As needed positive electrode collector 13 is arranged to contact with anode 12.In addition, as needed will Negative electrode collector 17 is arranged to contact with cathode 16.

Partition 20 is arranged to that the cathode chamber 24 of anode 12 and anode electrolyte 14 will be accommodated and is accommodated in closed container 22 26 zoning of anode chamber of cathode 16 and electrolyte liquid 18 is opened.Partition 20 has hydroxide ion conductibility, but does not have saturating It is aqueous.Herein, in this specification " do not have water penetration " and refer to by " fine and close sex determination test " used in aftermentioned example 1 or with Method on the basis of this or in the case where constituting evaluation water penetration, with measuring object (such as partition 20 and/or porous substrate 28) water of one side side contacts is not transmitted through another surface side.That is, partition 20, which does not have water penetration, means that partition 20 has not The high compaction of permeable degree, it is meant that be not the porous membrane or other porous materials with water penetration.Therefore, become pair It is physical that partition caused by the zinc dendrite generated when charging is prevented to run through, to prevent the short circuit of positive and negative interpolar extremely effective It constitutes.But naturally it is also possible to which porous substrate 28 is set up on partition 20 as shown in Figure 1.In short, because partition 20 has hydrogen-oxygen Compound ionic conductivity, so required hydroxide ion can have between anode electrolyte 14 and electrolyte liquid 18 It efficient moves, to realize the discharge and recharge reaction in cathode chamber 24 and anode chamber 26.It charges in cathode chamber 24 and anode chamber 26 When reaction it is as follows, exoelectrical reaction is in contrast.

Anode: Ni (OH)₂+OH^-→NiOOH+H₂O+e^-

Cathode: ZnO+H₂O+2e^-→Zn+2OH^-

Wherein, above-mentioned negative reaction is made of 2 reactions below.

The dissolution of-ZnO is reacted: ZnO+H₂O+2OH^-→Zn(OH)₄ ^2-

The evolution reaction of-Zn: Zn (OH)₄ ^2-+2e^-→Zn+4OH^-

Nickel-zinc cell 10 has side of the positive electrode remaining space 25, the appearance of the side of the positive electrode remaining space 25 preferably in cathode chamber 24 The amount of moisture that anode when product allows with charge and discharge is reacted and generated increases and decreases, also, has negative side remaining in anode chamber 26 Space 27, the amount of moisture that the volume of the negative side remaining space 27 allows negative reaction when adjoint charge and discharge and generates subtract increasing. Thus, it is possible to be effectively prevented the unfavorable condition generated by the amount of moisture increase and decrease in cathode chamber 24 and anode chamber 26 (such as to leak Container deformation etc. caused by liquid, container internal pressure change), further increase the reliability of nickel-zinc cell.That is, can by above-mentioned reaction equation Know, water increases in cathode chamber 24 when charging, and water is reduced in anode chamber 26.On the other hand, water is reduced in cathode chamber 24 when electric discharge, And water increases in anode chamber 26.For this point, for existing partition because nearly all having water penetration, water energy is enough via partition It frees in and out.But partition 20 used in the present invention is because of the structure for having the compactness without water penetration high, water It cannot be freed in and out via partition 20, with charge and discharge, in cathode chamber 24 and/or 26 Inner electrolysis liquid measure folk prescription of anode chamber increases Add, it may occur that a problem that leakage.Therefore, by having side of the positive electrode remaining space 25 in cathode chamber 24, the side of the positive electrode is surplus The amount of moisture that anode when the volume of complementary space 25 allows with charge and discharge is reacted and generated increases and decreases, as shown in Fig. 2, being capable of conduct The increased buffering of anode electrolyte 14 works when can cope with charging.That is, as shown in Fig. 2, side of the positive electrode remaining space after full charge 25 also work as buffering, thus it enables that increased anode electrolyte 14 does not overflow and is positively held in cathode chamber 24 It is interior.Similarly, by having negative side remaining space 27 in anode chamber 26, the volume of the negative side remaining space 27 allows companion Negative reaction when with charge and discharge and the amount of moisture generated subtracts increasing, can be increased as electrolyte liquid 18 when can cope with electric discharge Buffering works.

Cathode chamber 24 and the increase and decrease amount of the moisture in anode chamber 26 can be calculated based on reaction equation above-mentioned.By above-mentioned anti- Answer formula it is found that charging when anode 12 at H₂O production quantity is equivalent to the H at cathode 16₂2 times of O consumption.It therefore, can be with Keep the volumetric ratio negative side remaining space 27 of side of the positive electrode remaining space 25 big.In short, it is preferred that making the appearance of side of the positive electrode remaining space 25 Product is has several or more than needed to a certain degree volumes, to be not only contained in the moisture incrementss estimated in cathode chamber 24, moreover it is possible to The enough oxygen can be generated by anode 12 when the gases, overcharge such as air pre-existing in internal pressure appropriate receiving cathode chamber 24 Gas.For this point, although as long as it may be said that negative side remaining space 27 is identical as side of the positive electrode remaining space 25 as shown in Figure 1 The volume of degree, but when being constituted battery with last current state of discharging, being preferably provided with is more than the water reduction amount generated with charging Remaining space.In short, negative side remaining space 27 is because the increase and decrease amount of water only has the half degree in cathode chamber 24, it can With smaller than side of the positive electrode remaining space 25.

Nickel-zinc cell 10 is in the case where constructing under last current state of discharging, preferably: side of the positive electrode remaining space 25, which has, is more than Anode reaction and the volume of increased amount of moisture when estimating with charging, are not pre-charged in side of the positive electrode remaining space 25 Anode electrolyte 14, also, it is more than to estimate with negative reaction when charging and the water of reduction that negative side remaining space 27, which has, The volume of component is pre-charged with the electrolyte liquid 18 for estimating reduced amount in negative side remaining space 27.On the other hand, nickel Zinc battery 10 is in the case where constructing under fully charged state, preferably: it is more than to estimate with putting that side of the positive electrode remaining space 25, which has, Anode reaction and the volume of the amount of moisture of reduction when electric, are pre-filled in side of the positive electrode remaining space 25 and estimate reduced amount Anode electrolyte 14, also, negative side remaining space 27 have be more than estimate with electric discharge when negative reaction and it is increased The volume of amount of moisture is not pre-charged with electrolyte liquid 18 in negative side remaining space 27.

It is preferred that being not filled with anode 12 in side of the positive electrode remaining space 25 and/or being not filled in negative side remaining space 27 negative Pole 16, respectively without filling anode 12 and cathode 16 more preferably in side of the positive electrode remaining space 25 and negative side remaining space 27. In these remaining spaces, whens charge and discharge, can occur electrolyte caused by reducing because of amount of moisture and exhaust.That is, because surplus at these Even if also it can not be made sufficiently to participate in discharge and recharge reaction, so inefficent filled with positive 12, cathode 16 in complementary space.Cause This can be made by being not filled with anode 12 and cathode 16 respectively in side of the positive electrode remaining space 25 and negative side remaining space 27 Anode 12 and cathode 16 more efficiently and steadily participate in cell reaction without waste.

Nickel-zinc cell of the invention is preferably configured as the longitudinally disposed longitudinal type structure of partition.In the longitudinally disposed situation of partition Under, become cathode chamber/partition/anode chamber composition that laterally (horizontal direction) arranges.The feelings of longitudinally disposed partition 20 as shown in Figure 1 Under condition, typical scenario is: having side of the positive electrode remaining space 25 in the top of cathode chamber 24, also, has in the top of anode chamber 26 There is negative side remaining space 27.But using gelatinous electrolyte, even if electrolyte is reduced, it still is able to Electrolyte is kept in the discharge and recharge reaction part of cathode chamber 24 and/or anode chamber 26, so can also be in the top of cathode chamber 24 Part (such as lateral portions other than part (such as lateral portions or section below) and/or the top of anode chamber 26 in addition Or section below) side of the positive electrode remaining space 25 and/or negative side remaining space 27 are set, the freedom degree of design increases.

Alternatively, nickel-zinc cell of the invention is also configured to the cross structure that partition is laterally arranged.It is laterally set in partition In the case where setting, become the composition of cathode chamber/partition/anode chamber longitudinal (vertical direction) stacking.At this point, for example by using solidifying Gelatinous electrolyte can also remain contact of the partition with electrolyte even if electrolyte is reduced.Alternatively, it is also possible to constitute Are as follows: the water-absorbing resins such as non-woven fabrics or liquid retention resin are configured between anode and partition and/or between cathode and partition Electrolyte can also be maintained at positive and/or cathode even if in the case where electrolyte is reduced by second partition (resin separator) Discharge and recharge reaction part.As water-absorbing resins or the preference of liquid retention resin, polyolefin-based resins can be enumerated.In this way It can be in the part (such as lateral portions or section below) other than the top of cathode chamber and/or the portion other than the top of anode chamber Divide (such as lateral portions or section below) setting side of the positive electrode remaining space and/or negative side remaining space.

Partition

Partition 20 is the component for having hydroxide ion conductibility but not having water penetration, typically plate, membranaceous Or the form of stratiform.Partition 20 is arranged in closed container 22, will accommodate 24 He of cathode chamber of anode 12 and anode electrolyte 14 26 zoning of anode chamber for accommodating cathode 16 and electrolyte liquid 18 is opened.

Partition 20 is preferably formed by inorganic solid electrolyte body.The conductive nothing of hydroxide ion is used as partition 20 Thus the electrolyte of positive and negative interpolar is isolated, and ensures hydroxide ion conductibility by machine solid electrolytic plastid.Moreover, because It is typically fine and close and hard inoganic solids to constitute the inorganic solid electrolyte of partition 20, it is possible to physical prevention charging Partition caused by the zinc dendrite of Shi Shengcheng runs through, to prevent the short circuit of positive and negative interpolar.As a result, nickel zinc can be significantly increased The reliability of battery.Inorganic solid electrolyte body is preferably densified to the degree for not having water penetration.Such as inoganic solids electricity It is preferably 90% or more that plastid, which is solved, by the relative density that Archimedes method calculates, and more preferably 92% or more, further preferably It is 95% or more, as long as fine and close and hard to the inorganic solid electrolyte body for preventing the perforative degree of zinc dendrite and unlimited Due to this.Such fine and close and hard inorganic solid electrolyte body can be manufactured by hydro-thermal process.Therefore, do not pass through hydro-thermal The simple powder compact of processing is frangible in the solution because not fine and close, so simultaneously as inorganic solid electrolyte body of the invention It is undesirable.It is however also possible to, as long as fine and close and hard inorganic solid electrolyte body can be obtained, own without hydro-thermal process Preparation method can be used.

Partition 20 or inorganic solid electrolyte body can be comprising having the conductive inoganic solids of hydroxide ion Electrolyte and the particle group that constitutes and the complex for assisting the densification of these particle groups, cured auxiliary element.Alternatively, partition 20 are also possible to be precipitated as the open pore porous body of substrate and in hole and grow and fill the inorganic of the hole of the porous body The complex of solid electrolyte (such as layered double-hydroxide).As the example for the substance for constituting the porous body, can enumerate The insulating properties substances such as the ceramics such as aluminium oxide, zirconium oxide, the porous sheet formed by Foamex or fibrous material.

Inorganic solid electrolyte body is preferably comprised with general formula: M²⁺ _1-xM³⁺ _x(OH)₂A^n- _x/n·mH₂O (in formula, M²⁺For divalent Cation, M³⁺For the cation of trivalent, A^n-For the anion of n valence, the integer that n is 1 or more, x is that 0.1~0.4, m is any Real number) the layered double-hydroxide (LDH) formed substantially, more preferably formed by such LDH.In above-mentioned general formula, M²⁺It can Think arbitrary divalent cation, as preference, Mg can be enumerated²⁺、Ca²⁺And Zn²⁺, more preferably Mg²⁺。M³⁺It can be to appoint The trivalent cation of meaning, as preference, can enumerate Al³⁺Or Cr³⁺, more preferably Al³⁺。A^n-It can be arbitrary anion, As preference, OH can be enumerated^-And CO₃ ^2-.Therefore, in above-mentioned general formula, preferably M²⁺Include Mg²⁺、M³⁺Include Al³⁺、A^n-Include OH^-And/or CO₃ ^2-.The integer that n is 1 or more, preferably 1 or 2.X is 0.1~0.4, preferably 0.2~0.35.M is arbitrary Real number.More specifically, m is 0 or more, typically the real number or integer more than 0 or 1 or more.In addition, in above-mentioned general formula, it can With with the cation of 4 valences or higher valence mumber by M³⁺Part or all substitution, at this point, can also suitably change in above-mentioned general formula Anion A^n-Coefficient x/n.

Inorganic solid electrolyte body preferably passes through hydro-thermal process and implements densification.Hydro-thermal process is to the double hydroxides of stratiform Object, the one densification of especially Mg-Al type layered double-hydroxide are very effective.Implement densification for example such as by hydro-thermal process Patent document 1 (International Publication No. 2013/118561) is recorded, and the powder compact of pure water and plate is put into pressure vessel, 120~250 DEG C, preferably 180~250 DEG C at a temperature of carry out 2~24 hours, preferably 3~10 hours.Use hydro-thermal process More preferable manufacturing method is as described later.

Inorganic solid electrolyte body can be any form in plate, membranaceous or stratiform, membranaceous or lamellar morphologies In the case of, preferably by membranaceous or stratiform inorganic solid electrolyte body formed on porous substrate or in which.If it is plate shape State can then ensure sufficient compactedness, and more effectively zinc dendrite be prevented to run through.On the other hand, compare plate if it is thickness Thin membranaceous or stratiform the form of shape, then have the following advantages: can ensure against the knot that zinc dendrite runs through required bottom line Solidity, and the resistance of partition is reduced intentionally.The preferred thickness of the inorganic solid electrolyte body of plate is 0.01~0.5mm, more Preferably 0.02~0.2mm, further preferably 0.05~0.1mm.In addition, the hydroxide ion of inorganic solid electrolyte body Conductivity is more desirable, and typically has 10^-4~10^-1The conductivity of S/m.On the other hand, the case where membranaceous or lamellar morphologies Under, thickness be preferably 100 μm hereinafter, more preferably 75 μm hereinafter, further preferably 50 μm hereinafter, particularly preferably 25 μm with Under, most preferably 5 μm or less.By keeping it so thin, the low resistance of partition 20 can be realized.Because of the lower limit value root of thickness It is different according to purposes, so being not particularly limited, but in order to ensure as the knot required by separator membrane or layer to a certain degree Solidity, preferred thickness are 1 μm or more, more preferably 2 μm or more.

Porous substrate

Porous substrate 28 is equipped on the surface of 12 side of anode of partition 20.Because porous substrate 28 has water penetration, Anode electrolyte 14 and electrolyte liquid 18 can reach partition 20 certainly, but by there are porous substrate 28, can every Hydroxide ion is more stably kept on plate 20.In addition, also can because intensity can be assigned by porous substrate 28 Partition 20 enough is thinned and realizes low resistance.Alternatively, it is also possible on porous substrate 28 or in which formed inorganic solid electrolyte The dense film or compacted zone of body (preferably LDH).In the case where porous substrate is arranged in the single side of partition 20, consider to prepare more Hole substrate, the method that inorganic solid electrolyte forms a film on the porous substrate (this method is as described later).It should be noted that scheming In 1, porous substrate 28 is arranged in the whole face of the single side of partition 20, but may be to be provided only in the single side of partition 20 The composition in a part of (region for such as participating in discharge and recharge reaction).Such as on porous substrate 28 or in which by inorganic solid electrolyte In the case that plastid is formed as membranaceous or stratiform, because of its preparation method, typical scenario be partition 20 single side whole face be provided with it is more The composition of hole substrate 28.On the other hand, the inorganic solid electrolyte bodily form is become to the feelings of the plate of (not needing substrate) self-support Under condition, only a part in the single side of partition 20 (region for such as participating in discharge and recharge reaction) can be installed by porous substrate afterwards 28, rear in the whole face of single side porous substrate 28 can also be installed.

But in the case where only considering the performance of partition 20 and the respective function of porous substrate 28, consider porous substrate 28 The configuration (that is, form by the configuration of partition 20 in positive 12 sides) on the surface of 16 side of cathode of partition 20 is set, by porous base Configuration (that is, form by the configuration of partition 20 in 16 side of cathode) this 2 kinds configurations of 12 side of anode of partition 20 are arranged in material 28.So And in nickel-zinc cell 10 of the invention, use the configuration on the surface for 12 side of anode that porous substrate 28 is arranged in partition 20. At this point, partition 20 is located at the surface of 16 side of cathode of porous substrate 28, as a result, be located at the anode 12 of porous substrate 28 with partition 20 The case where surface of side, is compared, and several advantageous effects as shown below can be brought.

First, it can more effectively inhibit partition 20 (such as LDH dense film) to remove from porous substrate 28.That is, such as Figure 12 It is shown, in the case where reaching partition 20 by the growth zinc dendrite D of cathode 16, as the producible stress of the growth of zinc dendrite D exists Partition 20 is worked to the direction that porous substrate 28 pushes, as a result, partition 20 is not easy to remove from porous substrate 28.

Second, even if growing zinc dendrite D by cathode 16, also it is shown in Fig.12 the front end in anode 12 and cathode 16 A certain distance is ensured by porous substrate 28 always between (that is, front end of zinc dendrite D), as a result, can effectively inhibit or Postpone the short circuit of the zinc dendrite D developed from cathode 16 and anode 12.Moreover, because even just in case partition 20 damages, zinc branch Crystalline substance can continue to grow to the direction of anode 12, can also pass through thickness and porous structure (the especially porous knot of porous substrate 28 The detour of growth crack caused by structure) intentionally interfere the growth of zinc dendrite D, it is possible to inhibit or delay zinc dendrite D and The short circuit of anode 12.In addition, also it can be expected that inhibiting self discharge.

Third prevents the zinc dendrite D from cathode 16 to the structure of the intrusion of porous substrate 28 because becoming by partition 20 At, it is possible to avoid or inhibit the unfavorable condition that can occur with the zinc dendrite growth in porous substrate 28.That is, porous In substrate 28 in the case where growth zinc dendrite, the zinc dendrite growth pahtfinder hard adjoint according to the porous structure of porous substrate 28 It promotes.If at this point, zinc dendrite fall off and in the case where being electrically cut off from cathode 16, the zinc dendrite to fall off passivation and more It is blocked in hole substrate 28, it is possible to battery performance be caused to reduce.Zinc dendrite can be prevented to invade by partition 20 porous Such unfavorable condition is effectively prevented from or inhibited in substrate 28.

In addition, as set forth above, it is possible to configuring nonwoven between anode 12 and partition 20 and/or between cathode 16 and partition 20 The second partition (resin separator) of the water-absorbing resins such as cloth or liquid retention resin is even and if in the case where becoming electrolyte reduction Electrolyte can also be maintained to the composition of the reactive moieties of anode and/or cathode.As water-absorbing resins or liquid retention resin Preference can enumerate polyolefin-based resins.

Anode

Anode 12 includes nickel hydroxide and/or hydroxy nickel oxide.Such as nickel zinc is being constituted with electric discharge last current state shown in FIG. 1 In the case where battery, as long as nickel hydroxide is used as anode 12, nickel-zinc cell is being constituted with fully charged state shown in Fig. 2 In the case where, as long as hydroxy nickel oxide is used as anode 12.Nickel hydroxide and hydroxy nickel oxide (hereinafter referred to as nickel hydroxide Deng) it is the positive active material for being generally used for nickel-zinc cell, typically particle shape.It, can be in its crystalline substance in nickel hydroxide etc. Solid solution has the xenogenesis element other than nickel in lattice, and thus, it is possible to realize improvements in charge efficiency under high temperature.As such xenogenesis member The example of element, can enumerate zinc and cobalt.In addition, nickel hydroxide etc. can be mixed with cobalt set member, as such cobalt set member Example, the shot-like particle of metallic cobalt, cobalt/cobalt oxide (such as cobalt black) can be enumerated.It in turn, can also be by nickel hydroxide etc. The surface of particle (can be dissolved xenogenesis element) is coating with cobalt compound, as the example of such cobalt compound, Ke Yiju Out cobalt black, the α type cobalt hydroxide of divalent, divalent β type cobalt hydroxide, more than divalent high-order cobalt compound and they Any combination.

Positive 12 other than nickel hydroxide based compound and the xenogenesis element that can be solid-solubilized in nickel hydroxide based compound, Additional element can also be further included.As the example of such additional element, scandium (Sc), lanthanum (La), cerium can be enumerated (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), golden (Au) and mercury (Hg), And their any combination.Being not particularly limited containing form for additional element, can be with metallic monomer or metallic compound (example Such as oxide, hydroxide, halide and carbonated) form include.Metallic monomer or gold of the addition comprising additional element In the case where belonging to compound, relative to 100 parts by weight of nickel hydroxide based compound, additive amount is preferably 0.5~20 parts by weight, More preferably 2~5 parts by weight.

Anode 12 can also be configured to anode mixture ands further including electrolyte etc..Anode mixture can wrap hydrogeneous Conductive materials, the adhesives such as magnesium oxide-nickel series compound particles, electrolyte and the carbon particle that includes as needed etc..

It is preferred that positive electrode collector 13 is arranged to contact with anode 12.Positive electrode collector 13 can be as shown in Figure 1 through close It closes container 22 and extends to its outside, positive terminal is constituted by itself, or in or beyond closed container 22 and in addition The composition of the positive terminal connection of setting.As the preference of positive electrode collector 13, it is porous that the nickel systems such as foaming nickel plate can be enumerated Substrate.In this case, preferably for example by equably coating includes the electrode activities such as nickel hydroxide on nickel porous substrate The paste of substance simultaneously makes it dry to make the positive plate formed by positive 12/ positive electrode collector 13.At this point, it is also preferred that after to drying Positive plate (i.e. positive 12/ positive electrode collector 13) implement pressurized treatments, prevent electrode active material from falling off and improving electrode Density.

Cathode

Cathode 16 includes zinc and/or zinc oxide.It, can be with zinc gold as long as zinc has the electro-chemical activity for being suitble to cathode Belong to, any form in zinc compound and kirsite includes.As the preference of negative electrode material, zinc oxide, zinc can be enumerated Metal, calcium zincates etc., the more preferably mixture of zinc metal and zinc oxide.Cathode 16 is configured to gel, can also be with Electrolyte is mixed and made into cathode agent.Such as by adding electrolyte and tackifier in the negative active material, can be held The cathode of easy gelation.As the example of tackifier, polyvinyl alcohol, polyacrylate, CMC, alginic acid etc. can be enumerated, poly- third Olefin(e) acid because excellent to the chemical reagent resistance of highly basic, it is advantageous to.

As kirsite, can be used as not mercurous and lead kirsite known to mercuryless kirsite.Such as containing The indium of 0.01~0.06 mass %, the bismuth of 0.005~0.02 mass %, 0.0035~0.015 mass % the kirsite of aluminium have The effect for inhibiting hydrogen to generate, it is advantageous to.Especially indium, bismuth are advantageous in terms of making discharge performance raising.By kirsite The self-dissolving speed in alkaline electrolyte can be slowed down as cathode, so that hydrogen be inhibited to generate, improve safety.

The shape of negative electrode material is not particularly limited, be preferably made it is powdered so that surface area increase, cope with Heavy-current discharge.The average grain diameter of preferred negative electrode material is 90~210 μm of range in the case where kirsite, if Within the scope of this, then surface area is big, so being suitble to reply heavy-current discharge, and is easy equably to mix with electrolyte and gelating agent It closes, treatability when battery assembles is also good.

It is preferred that negative electrode collector 17 is arranged to contact with cathode 16.Negative electrode collector 17 can be as shown in Figure 1 through close It closes container 22 and extends to its outside, negative terminal is constituted by itself, or in or beyond closed container 22 and in addition The composition of the negative terminal connection of setting.As the preference of negative electrode collector 17, copper punch metal can be enumerated.Such case Under, for example, on copper punch metal coating is (such as poly- comprising Zinc oxide powder and/or zinc powder and desired adhesive Tetrafluoroethene particle) mixture, can suitably make the negative plate formed by 16/ negative electrode collector 17 of cathode.At this point, It is preferred that implementing pressurized treatments to the negative plate (i.e. 16/ negative electrode collector 17 of cathode) after drying, prevent electrode active material from falling off And improve electrode density.

Electrolyte

Anode electrolyte 14 and electrolyte liquid 18 include alkali metal hydroxide.That is, will include alkali metal hydroxide Aqueous solution be used as anode electrolyte 14 and electrolyte liquid 18.As the example of alkali metal hydroxide, hydrogen-oxygen can be enumerated Change potassium, sodium hydroxide, lithium hydroxide, ammonium hydroxide etc., more preferably potassium hydroxide.It, can be in order to inhibit the self-dissolving of kirsite The zinc compounds such as zinc oxide, zinc hydroxide are added in the electrolytic solution.As described above, anode electrolyte 14 and electrolyte liquid 18 can To be mixed with anode 12 and/or cathode 16, exist in the form of anode mixture and/or cathode agent.In addition, being electrolysed in order to prevent Liquid leakage, can be by Electrolyte Gel.As gelating agent, it is preferable to use the solvent of Electolyte-absorptive and the polymerization of swelling The polymer such as polyethylene oxide, polyvinyl alcohol, polyacrylamide, starch can be used in object.

Closed container

Closed container 22 is the closed container for accommodating anode 12, anode electrolyte 14, cathode 16 and electrolyte liquid 18, tool It is standby that there is fluid tight and air-tightness structure.As long as the material of closed container has the alkali metal hydroxides such as potassium hydroxide resistance to It is just not particularly limited by property, preferably the resins system such as polyolefin resin, ABS resin, Noryl, more preferably ABS tree Rouge or Noryl.Partition 20 can be fixed in various ways in closed container 22, preferably by potassium hydroxide etc. There is alkali metal hydroxide the adhesive of tolerance to be fixed.In addition, using the closed container 22 of polyolefin resin In the case of, it is also preferred that passing through heat bonding stationary barrier 20.

Laminated type nickel-zinc cell arranged side by side

Nickel-zinc cell 10 shown in FIG. 1 has 1 pair of anode 12 and cathode 16, or has 2 in closed container 22 To the composition of above anode 12 and cathode 16.In this case, preferably anode 12 and 16 alternating juxtaposition of cathode are configured to The nickel-zinc cell of laminated type arranged side by side.Fig. 3 is illustrated in by the one of such laminated type nickel-zinc cell arranged side by side.In Fig. 3, it is laminated side by side Type nickel-zinc cell 30 has the first cathode chamber 24a (positive electrode collector 13 for having one side coating anode 12)/partition 20/ first negative 20/ second cathode chamber 24b of pole room 26a (negative electrode collector 17 for having double spread cathode 16)/partition (is having double spread just The positive electrode collector 13 of pole 12) 20/ second anode chamber 26b (negative electrode collector 17 for having double spread cathode 16) of/partition/every Composition made of 20/ third cathode chamber 24c (positive electrode collector 13 for having one side coating anode 12) of plate is arranged successively.It should say It is bright, in Fig. 3, because cathode chamber 24a, 24b and the constituent element of 24c are identical as the constituent element of cathode chamber 24 of Fig. 1, Symbol identical with Fig. 1 is assigned, because of the constituent element phase of the constituent element of anode chamber 26a and 26b and the anode chamber 26 of Fig. 1 Together, so assigning symbol identical with Fig. 1.Cathode chamber, partition and anode chamber are repeated in desired number like this And it is appropriately configured, it is possible thereby to constitute the laminated type nickel-zinc cell arranged side by side for the anode and cathode for having desired quantity.

It is accompanied with the LDH partition of porous substrate

As described above, the inorganic solid electrolyte body for constituting partition in the present invention can be membranaceous or stratiform form.This In the case of kind, be preferably made membranaceous or stratiform inorganic solid electrolyte body formed on porous substrate or in which, be accompanied with The partition of porous substrate.The particularly preferred partition for being accompanied with porous substrate has porous substrate and is formed on the porous substrate And/or the carrier ring in porous substrate, carrier ring include layered double-hydroxide above-mentioned (LDH).Carrier ring does not have permeable Property.That is, porous material because hole there are due to can have water penetration, but carrier ring densified by LDH it is permeable to not having The degree of property.Carrier ring is preferably formed as on porous substrate.Such as shown in Fig. 4, preferably with LDH dense film on porous substrate 28 Form formed carrier ring 20.In this case, from the point of view of the property of porous substrate 28, naturally it is also possible to as shown in figure 4, more LDH is also formed in the surface of hole substrate 28 and its neighbouring hole.Alternatively, can also be as shown in Figure 5, in porous substrate 28 In (such as in the surface and its neighbouring hole of porous substrate 28) LDH densely be formed, thus make at least the one of porous substrate 28 Part constitutes carrier ring 20 '.For this point, embodiment shown in fig. 5 is the carrier ring for eliminating Fig. 4 illustrated embodiment Composition obtained by the part of film is equivalent in 20, but not limited to this, as long as carrier ring is parallel with the surface of porous substrate 28 In the presence of.In short, can obtain because carrier ring is densified by LDH to the degree for not having water penetration with hydroxide Object ionic conductivity but the peculiar function of not having water penetration.

Porous substrate is preferably able on it and/or wherein form the substrate of the carrier ring containing LDH, to its material, porous Structure is not particularly limited.Forming the carrier ring containing LDH on porous substrate and/or in porous substrate is typical scenario, but The carrier ring containing LDH can be formed in nonporous substrate, then by various known methods by nonporous substrate porous.In short, Porous substrate has the porous structure with water penetration, and can constitute electrolyte when being installed in battery as battery separator can The structure for reaching carrier ring is from this viewpoint preferred.

Porous substrate is preferably made of at least one kind of in ceramic material, metal material and high molecular material.Porous base Material is more preferably made of ceramic material.In this case, as the preference of ceramic material, can enumerate aluminium oxide, zirconium oxide, Titanium dioxide, magnesia, spinelle, calcium oxide, cordierite, zeolite, mullite, ferrite, zinc oxide, silicon carbide, nitrogen Change aluminium, silicon nitride and their any combination, more preferably aluminium oxide, zirconium oxide, titanium dioxide and their any combination, it is special It You Xuanwei not aluminium oxide and zirconium oxide, most preferably aluminium oxide.When using these porous ceramics, compactness easy to form is excellent Carrier ring containing LDH.As the preference of metal material, aluminum and zinc can be enumerated.It, can be with as the preference of high molecular material Enumerate polystyrene, polyether sulfone, polypropylene, epoxy resin, polyphenylene sulfide and their any combination.More preferably from above-mentioned various The tolerance to the electrolyte of battery, the i.e. excellent material of alkali resistance are suitably selected as in preferred material.

The average air aperture of porous substrate is preferably 0.001~1.5 μm, more preferably 0.001~1.25 μm, further excellent It is selected as 0.001~1.0 μm, particularly preferably 0.001~0.75 μm, most preferably 0.001~0.5 μm.By for such model It encloses, it can be ensured that porous substrate has desired water penetration and forms densification to the degree without water penetration containing LDH Carrier ring.It, can be by measuring gas based on the electron microscope on the surface of porous substrate (SEM) image in the present invention The longest distance in hole carries out the measurement in average air aperture.The multiplying power of electron microscope used in the measurement (SEM) image is 20000 times, obtained whole stomata diameters are arranged by size order, it is below to be averaged the 15 above numerical value peace mean values 15 numerical value add up to each visual field to take 30 numerical value, calculate the average value in 2 visuals field, available average air aperture.Survey length When, the long function of survey, image analysis software (such as Photoshop, Adobe corporation) of the software of SEM etc. can be used.

The surface of porous substrate preferably has 10~60% porosity, more preferably 15~55%, further preferably 20~50%.By for such range, it can be ensured that porous substrate has desired water penetration and formed fine and close to not The carrier ring containing LDH of degree with water penetration.It herein, is because being easy to use using the porosity on the surface of porous substrate Following image procossings carry out porosity measurement, and it may be said that the porosity on the surface of porous substrate substantially represents porous base The porosity inside material.That is, it can be said that if the surface of porous substrate be it is fine and close, the inside of porous substrate similarly be cause Close.In the present invention, the porosity on the surface of porous substrate can be measured as described below by using the method for image procossing. That is, 1) electron microscope (SEM) image (10000 times of multiplying power or more) on porous substrate surface is obtained, and 2) use Photoshop Image analysis softwares such as (Adobe corporations), read the SEM image of tonal gradation, and 3) press [image] → [tonal correction] → [two Value] sequentially built black and white bianry image, 4) with pixel number shared by black portions divided by whole pixel number institutes of image The value obtained is the porosity (%).It should be noted that carrying out the measurement of the porosity preferably to porous substrate surface by the image procossing The region of 6 μm of 6 μ m carry out, in order to make its more objective index, more preferably use obtains region at optional 3 The porosity average value.

Carrier ring is formed on porous substrate and/or in porous substrate, is preferably formed as on porous substrate.Such as Fig. 4 institute Show, in the case that carrier ring 20 is formed on porous substrate 28, carrier ring 20 is the form of LDH dense film, the LDH dense film Typical case be to be formed by LDH.In addition, as shown in figure 5, in the case that carrier ring 20 ' is formed in porous substrate 28, more LDH densely be formed (typically in the surface of porous substrate 28 and its neighbouring hole) in hole substrate 28, so carrier ring 20 ' typically by porous substrate 28 at least part and LDH formed.Carrier ring 20 ' shown in fig. 5 can by grinding, The known methods such as cutting remove the part for being equivalent to film in carrier ring 20 shown in Fig. 4 and obtain.

Carrier ring does not have water penetration.Such as carrier ring is waterproof contacting one week with water for 25 DEG C even if single side.That is, every Plate layer is densified by LDH to the degree for not having water penetration.But, local in functional membrane and/or contingently saturating in the presence of having In the case where aqueous defect, it can also be repaired by filling the defect with healant appropriate (such as epoxy resin etc.) Ensure impermeability, such healant is not necessarily to hydroxide ion conductibility.In short, carrier ring is (typical Be LDH dense film) surface preferably there is 20% porosity below, more preferably 15% hereinafter, further preferably 10% hereinafter, particularly preferably 7% or less.The porosity on the surface of carrier ring is lower, it is meant that carrier ring (typically LDH Dense film) compactness it is higher, be preferred.It herein, is because being easy using following using the porosity on the surface of carrier ring Image procossing carries out porosity measurement, and the porosity on the surface of carrier ring is it may be said that substantially represent the stomata inside carrier ring Rate.That is, it can be said that if the surface of carrier ring be it is fine and close, the inside of carrier ring is similarly fine and close.In the present invention, every The porosity on the surface of plate layer can be measured as described below by using the method for image procossing.That is, 1) obtain partition layer surface Electron microscope (SEM) image (10000 times of multiplying power or more), 2) use the image analysis such as Photoshop (Adobe corporation) Software, reads the SEM image of tonal gradation, and 3) press the two of [image] → [tonal correction] → [binaryzation] sequentially built black and white Be worth image, 4) with pixel number shared by black portions divided by image whole pixel numbers it is resulting value for the porosity (%).It should Illustrate, preferably the region of 6 μm of 6 μ m of partition layer surface is carried out by the measurement that the image procossing carries out the porosity, in order to Make its more objective index, more preferably using the average value of the porosity obtained to region at optional 3.

Layered double-hydroxide is preferably made of the aggregate of multiple platy particles (i.e. LDH platy particles), multiple plate Shape particle is orientated to their the plate face direction for intersecting or obliquely intersecting substantially vertical with surface (substrate surface) of porous substrate. For embodiments thereof, as shown in figure 4, in the case where forming carrier ring 20 in the form of LDH dense film on porous substrate 28, The embodiment is particularly preferred and achievable, but as shown in figure 5, (typically in porous substrate in porous substrate 28 In 28 surface and its neighbouring hole) LDH densely be formed, so that at least part of porous substrate 28 constitutes carrier ring In the case where 20 ', also it can be achieved on.

I.e., it is known that LDH crystallizes the form for including the platy particles with layer structure shown in fig. 6, above-mentioned substantially vertical Or inclined orientation is extremely advantageous characteristic for the carrier ring (such as LDH dense film) containing LDH.This is because after orientation The carrier ring (such as orientation LDH dense film) containing LDH there is conductivity anisotropy, that is, the side that LDH platy particles are orientated It is significantly higher than the conductivity in perpendicular direction to the hydroxide ion conductivity in (i.e. the direction parallel with LDH layers).It is practical On, the inventors of the present invention have found the conductivity (S/cm) of the differently- oriented directivity side more vertical than with differently- oriented directivity in the orientation block of LDH To high 1 digit of conductivity (S/cm).That is, the above-mentioned substantially vertical or inclined orientation in the carrier ring of the invention containing LDH The conductivity anisotropy that LDH orientation body is had (is hung down with the surface of carrier ring or porous substrate in thickness direction Straight direction) it brings into play to greatest extent or intentionally, as a result, it can to greatest extent or intentionally improve the biography in thickness direction Conductance.Moreover, because there is the carrier ring containing LDH layer form can be realized low resistance compared with the LDH of block shape.Tool There is the carrier ring containing LDH of such orientation to be easy to conduct hydroxide ion in thickness direction.Moreover, because fine and close Change, so being extremely suitable for requiring the partition on thickness direction with high conductance and compactness.

LDH platy particles are in generally vertical direction height in carrier ring (typically LDH dense film) particularly preferably containing LDH Degree orientation.This is height-oriented to confirm in the following way: being measured using X-ray diffraction method to the surface of carrier ring In the case where, essentially without detecting the peak of (003) crystal face, or peak ratio (012) crystal face of (003) crystal face detected Peak it is weak (still, using with the peak same position due to (012) crystal face at observe the porous substrate of diffraction maximum the case where Under, because the peak of (012) crystal face due to LDH platy particles can not be determined, it is not limited thereto).This feature peak is special Property indicate that the LDH platy particles for constituting carrier ring (vertical direction or are similar to relative to carrier ring generally perpendicular direction Vertical inclined direction, preferred vertical) orientation.That is, although the peak of known (003) crystal face is the LDH powder to No yield point Highest peak observed by the case where progress X-ray diffraction, but in the case where the carrier ring of the LDH containing orientation, by making LDH Platy particles are orientated relative to carrier ring generally perpendicular direction, essentially without the peak for detecting (003) crystal face, Huo Zhejian The peak of peak ratio (012) crystal face of (003) crystal face measured is weak.This is because c-axis direction (00l) crystal face belonging to (003) crystal face (l is 3 and 6) is the face parallel with the layer structure of LDH platy particles, so, if the LDH platy particles are relative to partition Layer generally perpendicular direction orientation, then as a result LDH layer structure is passing through X-ray diffraction method also towards generally perpendicular direction In the case where measuring partition layer surface, the peak of (00l) crystal face (l is 3 and 6) does not occur or is difficult to occur.Especially (003) is brilliant There is following tendency at the peak in face, that is, will be than the peak intensity of (006) crystal face in the case where the peak that there is (003) crystal face, it is possible to It says compared with the peak of (006) crystal face, whether be easy evaluation in generally perpendicular direction has orientation.Therefore, the partition of the LDH containing orientation Layer is weak and dark essentially without the peak at the peak for detecting (003) crystal face or peak ratio (012) crystal face of (003) crystal face detected Show in the height-oriented of vertical direction, it is possible to say that this is preferred.

The thickness of carrier ring be preferably 100 μm hereinafter, more preferably 75 μm hereinafter, further preferably 50 μm hereinafter, special Not You Xuanwei 25 μm hereinafter, most preferably 5 μm or less.By keeping it so thin, the low resistance of partition can be realized.Carrier ring It is preferred that being formed on porous substrate as LDH dense film, in this case, the thickness of carrier ring is equivalent to LDH dense film Thickness.In addition, the thickness of carrier ring is equivalent to by porous substrate at least in the case that carrier ring is formed in porous substrate The thickness for the composite layer that a part and LDH are formed, carrier ring are formed on porous substrate and in situation therein, and LDH is equivalent to The overall thickness of dense film and above-mentioned composite layer.In short, can be realized if it is such thickness suitable for battery use etc. Desired low resistance.Because the lower limit value of the thickness of LDH alignment films is different depending on the application, it is not particularly limited, But in order to ensure as the compactedness required by the functional membranes such as partition to a certain degree, preferred thickness is 1 μm or more, more preferably 2 μm or more.

The above-mentioned LDH partition for being accompanied with porous substrate can manufacture as follows: (1) preparing porous substrate, (2) soak porous substrate Stain is in aqueous solution of raw material, and the aqueous solution of raw material is with the total concentration of 0.20~0.40mol/L (Mg containing magnesium ion²⁺) and aluminium ion (Al³⁺), and include urea, (3) carry out hydro-thermal process to porous substrate in aqueous solution of raw material, make comprising the double hydroxides of stratiform The carrier ring of object is formed on porous substrate and/or in porous substrate.

(1) preparation of porous substrate

As described above, porous substrate is preferably by least one kind of structure in ceramic material, metal material and high molecular material At.Porous substrate is more preferably made of ceramic material.In this case, as the preference of ceramic material, oxidation can be enumerated Aluminium, zirconium oxide, titanium dioxide, magnesia, spinelle, calcium oxide, cordierite, zeolite, mullite, ferrite, zinc oxide, Silicon carbide, aluminium nitride, silicon nitride and their any combination, more preferably aluminium oxide, zirconium oxide, titanium dioxide and their times Meaning combination, particularly preferably aluminium oxide and zirconium oxide, most preferably aluminium oxide.When using these porous ceramics, exists and be easy to mention The tendency of the compactness of carrier ring of the height containing LDH.Using the porous substrate of ceramic material, preferably to porous base Material is implemented ultrasonic cleaning, is cleaned with ion exchange water.

On the other hand, in the case where using high molecular material, preferably preparation surface is by the polymer base material of anionic.It is logical The core for making surface anionic in subsequent handling the group from anion to generate LDH is crossed, LDH plate grain can be promoted Son grows and is orientated to generally vertical direction.As long as surface by the polymer base material of anionic by known method to can yin The polymer base material of ionization carries out anionic processing and is subject to preparation.It is preferred that being assigned by the surface to polymer base material Give the slave SO that can be obtained as the anion of LDH₃ ^-(sulfonation), OH^-(hydroxylating) and CO₂ ^-At least one selected in (carboxylated) It plants and carries out anionic processing, more preferably sulfonation.It is capable of the polymer base material of anionic preferably as the electricity to battery It solves the tolerance of liquid and there is alkali resistance.The polymer base material for capableing of anionic preferably comprises from polystyrene, polyether sulfone, gathers Propylene, epoxy resin, at least one selected in polyphenylene sulfide, these polymer base materials are particularly suitable for sulfonation.It is especially fragrant Family polymer base material is preferred because being easy anionic (especially sulfonation), and such aromatic system polymer base material for example wraps Containing at least one selected from polystyrene, polyether sulfone, epoxy resin, polyphenylene sulfide, polystyrene is most preferably comprised.It carries out In the case that sulfonation is handled, if will the polymer base material of sulfonation be immersed in sulfuric acid (such as concentrated sulfuric acid), oleum, chlorine Sulfonic acid, sulfuric anhydride etc. are capable of in the acid of sulfonation, also can use other sulfonation technologies.Dipping in the acid for capableing of sulfonation As long as being carried out under room temperature or high temperature (such as 50~150 DEG C).In the case where using aromatic system polymer base material, by sulphur The aromatic system polymer base material of change the total reflection measuring method (ATR) by Fourier transformation type infrared spectroscopy (FT-IR) come In the case where measuring its surface, the 1601cm of phenyl CC stretching vibration is derived from transmitted spectrum^-1The transmittance values T at place₁₆₀₁Divided by Derived from sulfonic 1127cm^-1The transmittance values T at place₁₁₂₇Obtained from value T₁₆₀₁/T₁₁₂₇Preferably 0.920 or more, more preferably 0.930 or more, further preferably 0.940 or more.In transmitted spectrum, in 1601cm^-1The transmissivity at the extinction peak that place observes Value T₁₆₀₁It is all identical value regardless of whether there is sulfonic group because being derived from phenyl CC stretching vibration, and in 1127cm^-1 The transmittance values T at the extinction peak that place observes₁₁₂₇Because being derived from sulfonic group, the density of sulfonic acid is higher, is worth lower.Cause This, T₁₆₀₁/T₁₁₂₇Value it is bigger, more densely there are multiple sulfonic groups on the surface of polymer base material, can give birth to high-density At: core of the sulfonic group as the LDH of intermediate layer anion is introduced, the densification of the carrier ring containing LDH is facilitated.Therefore, exist When by polymer base material sulfonation, the time impregnated in the acid for capableing of sulfonation by appropriate adjustment can make above-mentioned T₁₆₀₁/T₁₁₂₇ Value within the above range.Such as in the case where using concentrated sulfuric acid progress sulfonation processing, preferably dip time is 6 days or more, more Preferably 12 days or more.The polymer base material for implementing anionic like this is preferably cleaned with ion exchange water, then in room It is dry under temperature or high temperature (such as 30~50 DEG C).

(2) dipping in aqueous solution of raw material

Next, porous substrate is immersed in aqueous solution of raw material with desired direction (such as horizontally or vertically).It will Porous substrate level keep in the case where, only need to by suspention, suspension, contacted with container bottom in a manner of configure porous substrate i.e. Can, such as porous substrate can be fixed with being suspended to the state in aqueous solution of raw material from container bottom.By porous substrate It, can be by the vertically disposed fixture of porous substrate as long as being arranged in container bottom in the case where vertical holding.In short, it is preferred that Make LDH on porous substrate with generally vertical direction or close to vertical direction (i.e. plate face of the LDH platy particles towards them The direction intersected or obliquely intersect substantially vertical with surface (substrate surface) of porous substrate) growth composition or configuration.Raw material Aqueous solution includes magnesium ion (Mg with defined total concentration²⁺) and aluminium ion (Al³⁺), and include urea.It is urinated by existing Element can generate in the solution ammonia using hydrolysis of urea, thus improve pH value, the metal ion coexisted be made to form hydroxide Object, so as to obtain LDH.In addition, because with hydrolysis generate carbon dioxide, can obtain anion be carbonate from The LDH of subtype.The magnesium ion and aluminum ions total concentration (Mg that aqueous solution of raw material is included²⁺+Al³⁺) be preferably 0.20~ 0.40mol/L, more preferably 0.22~0.38mol/L, further preferably 0.24~0.36mol/L, particularly preferably 0.26 ~0.34mol/L.If it is the concentration in such range, it can balance and carry out karyogenesis and crystalline growth, energy well Access that not only orientation is excellent but also the compactness also excellent carrier ring containing LDH.I.e., it is believed that if magnesium ion and aluminium ion Total concentration it is low, then compared with karyogenesis, crystalline growth is top dog, population reduce, particle size increase, and if The total concentration is high, then compared with crystalline growth, karyogenesis is top dog, and population increases, and particle size reduces.

It is preferred that magnesium nitrate and aluminum nitrate are dissolved in aqueous solution of raw material so that aqueous solution of raw material in addition to magnesium ion and Aluminium ion also includes nitrate ion.In this case, in aqueous solution of raw material, urea is relative to nitrate ion (NO₃ ^-) rub You are than (urea/NO₃ ^-) it is preferably 2~6, more preferably 4~5.

(3) carrier ring containing LDH is formed by hydro-thermal process

Hydro-thermal process is carried out to porous substrate in aqueous solution of raw material, is formed on porous substrate and/or in porous substrate Carrier ring containing LDH.The hydro-thermal process carries out preferably in closed container and at 60~150 DEG C, and more preferably 65~120 DEG C, further preferably 65~100 DEG C, particularly preferably 70~90 DEG C.As long as the ceiling temperature of hydro-thermal process selects porous base Material (such as polymer base material) is notheated the temperature of the degree of deformation.Heating rate when hydro-thermal process does not limit especially It is fixed, such as can be 10~200 DEG C/h, preferably 100~200 DEG C/h, more preferably 100~150 DEG C/h.Hydro-thermal process when It is suitably determined between as long as according to the target density of the carrier ring containing LDH and target thickness.

It is preferred that taking out porous substrate from closed container after hydro-thermal process, cleaned with ion exchange water.

The LDH platy particles high compaction of the carrier ring containing LDH in the composite material containing LDH manufactured as described above Change, and is orientated to the advantageous generally vertical direction of conduction.Therefore, it can be said that be extremely applicable to zinc dendrite develops into reality With the nickel-zinc cell for changing maximum barrier.

But the carrier ring containing LDH obtained by the above-mentioned manufacture method can be formed in the two sides of porous substrate.Cause This, in order to which the composite material for containing LDH to be made to be suitable as the form of partition, to the one of porous substrate preferably after film forming The carrier ring containing LDH in face carries out mechanical grinding, or takes and cannot form arranging for the carrier ring containing LDH in one side when film forming It applies.

The manufacturing method of LDH dense plates

The preferred configuration of inorganic solid electrolyte as plate can enumerate layered double-hydroxide (LDH) dense body. LDH dense body can be made by all methods, be illustrated below to an embodiment of preferable production process.The system It makes method to carry out as follows: will form and be burnt into using hydrotalcite as the raw material powder of the LDH of representative and oxide sintered body is made, it will After it is regenerated as layered double-hydroxide, extra moisture is removed.It, can easy and steadily offer and manufacture according to this method The high-grade layered double-hydroxide dense body that relative density is 88% or more.

(1) preparation of raw material powder

Prepare general formula: M²⁺ _1-xM³⁺ _x(OH)₂A^n- _x/n·mH₂O (in formula, M²⁺For the cation of divalent, M³⁺For trivalent sun from Son, A^n-For the anion of n valence, the integer that n is 1 or more, x be that 0.1~0.4, m is arbitrary real number) shown in stratiform pair hydrogen-oxygens The powder of compound is as raw material powder.In above-mentioned general formula, M²⁺It can be arbitrary divalent cation, as preference, can enumerate Mg²⁺、Ca²⁺And Zn²⁺, more preferably Mg²⁺。M³⁺It can be arbitrary trivalent cation, as preference, Al can be enumerated³⁺Or Cr³⁺, more preferably Al³⁺。A^n-OH can be enumerated as preference for arbitrary anion^-And CO₃ ^2-.Therefore, above-mentioned General formula preferably at least M²⁺Include Mg²⁺、M³⁺Include Al³⁺、A^n-Include OH^-And/or CO₃ ^2-.N be 1 or more integer, preferably 1 or 2.X is 0.1~0.4, preferably 0.2~0.35.Such raw material powder can be commercially available layered double-hydroxide product, It can be the raw material made by using known methods such as the liquid phase synthesizing methods of nitrate or chloride.The partial size of raw material powder As long as desired layered double-hydroxide dense body can be obtained, and there is no limit, volume reference D50 average grain diameter is preferably 0.1 ~1.0 μm, more preferably 0.3~0.8 μm.This is because when the partial size of raw material powder is meticulous, powder is easy cohesion, and when molding is residual A possibility that staying stomata is high；When excessive, mouldability is deteriorated.

Oxide powder can be made in raw material powder pre-burning as needed.Calcined temperature at this time is according to the M of composition²⁺ And M³⁺And have differences, preferably 500 DEG C hereinafter, more preferably 380~460 DEG C, the region that raw material particle size does not significantly change into Row.

(2) production of formed body

Raw material powder molding is obtained into formed body.The molding preferably press molding after and be burnt into before formed body (hereinafter referred to as For formed body) relative density be 43~65%, more preferably 45~60%, further preferably 47%~58%, utilize example It is carried out such as extrusion forming.The relative density of formed body is to calculate density by the size and weight of formed body, divided by theoretical density And find out, but the weight of formed body is by adsorption moisture because influenced, in order to obtain unique value, preferably to using The relative density of formed body made of storage 24 hours or more raw material powders in room temperature, the drier below of relative humidity 20% It is measured or relative density is measured after storing formed body under the above conditions.But by raw material powder pre-burning And in the case where oxide powder is made, the relative density of formed body is preferably 26~40%, and more preferably 29~36%.It should Illustrate, relative density when using oxide powder acquires as follows: assuming that constituting each metal member of layered double-hydroxide Procatarxis pre-burning and become oxide respectively, reduction density is found out as each hopcalite, using the reduction density as denominator And it finds out.The extrusion forming enumerated as an example can use the compacting of mold single shaft and carry out, and also can use cold isostatic pressing (CIP) it carries out.In the case where using cold isostatic pressing (CIP), preferably raw material powder is put into rubber container and carries out vacuum Sealing uses preform.Furthermore, it is possible to the method well known to injection forming, extrusion molding etc. is formed, about at Type method is not particularly limited.But it in the case that oxide powder is made in raw material powder pre-burning, is defined in dry formed Method.The relative density of these formed bodys not only has an impact to the intensity of obtained dense body, but also to usually with plate-like shape The degree of orientation of layered double-hydroxide also have an impact, it is therefore preferable that considering its purposes etc. and suitably setting within the above range Relative density when molding.

(3) firing process

Formed body obtained in above-mentioned operation is burnt into and obtains oxide sintered body.Oxide is preferably pressed in the firing The weight of sintered body be the 57~65% of the weight of formed body and/or volume be formed body volume 70~76% and carry out. It is not easily generated when subsequent handling is regenerated as layered double-hydroxide to regenerate if it is 57% or more of the weight of formed body Out-phase；If it is 65% hereinafter, being then sufficiently burnt into and fully being densified in subsequent handling.In addition, if it is molding 70% or more of the volume of body, then subsequent handling is regenerated as out-phase not easily generated when layered double-hydroxide, and is also not easy to produce Raw crackle；If it is 76% hereinafter, being then sufficiently burnt into and fully being densified in subsequent handling.By raw material powder pre-burning In the case where oxide powder is made, the 90% of the 85~95% of the weight of formed body and/or the volume of formed body is preferably obtained Above oxide sintered body.No matter whether raw material powder is by pre-burning, it is preferably to be burnt into and change for oxide sintered body by oxide The relative density of calculation is 20~40%, more preferably 20~35%, further preferably 20~30%.Herein, it is changed by oxide The relative density of calculation acquires as follows: assuming that constitute each metallic element of layered double-hydroxide becomes oxygen because of firing respectively Compound finds out reduction density as each hopcalite, finds out relative density using the reduction density as denominator.For Preferred firing temperature to oxide sintered body is 400~850 DEG C, more preferably 700~800 DEG C.It is preferred that in the range It is kept for 1 hour or more under firing temperature, the preferred retention time is 3~10 hours.In addition, in order to prevent because of heating sharply Release moisture, carbon dioxide and formed body is cracked, for making it reach the heating of above-mentioned firing temperature preferably with 100 DEG C/h Speed below carries out, more preferably 5~75 DEG C/h, further preferably 10~50 DEG C/h.Therefore, from be warming up to cooling (100 DEG C or less) total firing time preferably ensure that at 20 hours or more, more preferably 30~70 hours, further preferably 35~65 Hour.

(4) it is regenerated as the process of layered double-hydroxide

Oxide sintered body obtained in above-mentioned operation is maintained at the above-mentioned anion (A comprising n valence^n-) aqueous solution in Or it is regenerated as layered double-hydroxide right above aqueous solution, thus obtain the layered double-hydroxide solidified body rich in moisture. That is, the layered double-hydroxide solidified body obtained using the preparation method necessarily includes extra moisture.It should be noted that being wrapped in aqueous solution The anion contained can be the anion of the same race with the anion that includes in raw material powder, or different types of yin from Son.Holding of the oxide sintered body in aqueous solution or right above aqueous solution utilizes hydrothermal synthesis method preferably in closed container Carry out, as the example of such closed container, the closed container of Teflon (registered trademark) system can be enumerated, more preferably its Outside has the closed container of the casings such as stainless steel.Layered double-hydroxideization preferably carries out as follows: by oxide sintered body At 20 DEG C more than or lower than at 200 DEG C, kept with the state that at least one side of oxide sintered body is contacted with aqueous solution, more Preferred temperature is 50~180 DEG C, and further preferred temperature is 100~150 DEG C.It is preferred that in such layered double-hydroxide It is kept for oxidate sintered body 1 hour or more at a temperature of change, more preferably 2~50 hours, further preferably 5~20 hours.Such as Fruit is such retention time, then it can be made sufficiently to be regenerated as layered double-hydroxide and avoid or reduce out-phase residual.It answers Explanation is given, the retention time, there is no problem too long, sets in due course as long as paying attention to efficiency.

It is false as the anion species for the aqueous solution for being regenerated as the anion comprising n valence that layered double-hydroxide uses Surely in the case where being the carbon dioxide (carbanion) in air, ion exchange water can be used.It should be noted that in closed container When interior hydro-thermal process, oxide sintered body can be made to submerge in aqueous solution, also can be used fixture at least one side with it is water-soluble The state of liquid contact is handled.In the case where the state processing contacted at least one side with aqueous solution, because not having with complete water It is less compared to extra amount of moisture, so subsequent handling is completed in a short time sometimes.But it because is easy when aqueous solution is very few It cracks, it is advantageous to use and the same above moisture of firing body weight.

(5) dehydration procedure

Extra moisture is removed from the layered double-hydroxide solidified body for being rich in moisture obtained in above-mentioned operation.In this way Layered double-hydroxide dense body of the invention can be obtained.The process of the extra moisture of the removing is preferably in 300 DEG C or less, removing It is carried out under the environment of 25% or more presumption relative humidity under the maximum temperature of process.Moisture is from the double hydroxides of stratiform in order to prevent It is sharp evaporated in object solidified body, in the case where being dehydrated at temperatures greater than room temperature, preferably encloses again and be regenerated as stratiform pair It is carried out in closed container used in the step for regeneration of hydroxide.Preferable temperature at this time is 50~250 DEG C, further preferably It is 100~200 DEG C.In addition, preferred relative humidity when dehydration is 25~70%, further preferably 40~60%.It can To be dehydrated at room temperature, relative humidity at this time as long as in common indoor environment 40~70% in the range of as long as do not have It is problematic.

Embodiment

The present invention is further specifically described by example below.

Example 1: it is accompanied with the production and evaluation of the LDH partition of porous substrate

(1) production of porous substrate

Boehmite (Sasol corporation, DISPAL 18N4-80), methylcellulose and ion exchange water are pressed into (Bo Mu Stone): (methylcellulose): the mass ratio of (ion exchange water) is that 10:1:5 is weighed, and is then kneaded.Use manual pressure Power machine carries out extrusion forming to obtained mixture, is shaped to size well beyond 5cm × 8cm and with a thickness of the plate of 0.5cm. It by obtained formed body after 80 DEG C 12 hours dry, is burnt into 3 hours at 1150 DEG C, obtains oxidation aluminum porous substrate.By this The porous substrate cutting off processing that sample obtains at 5cm × 8cm size.

The porosity on porous substrate surface, knot are measured by using the method for image procossing for obtained porous substrate Fruit is 24.6%.The measurement of the porosity carries out as follows: 1) using scanning electron microscope (SEM, JSM-6610LV, JEOL Corporation), surface micro-structure is observed with the acceleration voltage of 10~20kV, obtains the electron microscope (SEM) on porous substrate surface Image (10000 times of multiplying power or more), 2) using image analysis softwares such as Photoshop (Adobe corporations), read tonal gradation SEM image, 3) press the bianry image of [image] → [tonal correction] → [binaryzation] sequentially built black and white, 4) by black part Pixel number shared by point is used as the porosity (%) divided by the resulting value of total pixel number of image.To 6 μ ms 6 on porous substrate surface μm region implement the measurement of the porosity.It should be noted that the SEM image on porous substrate surface is shown in Fig. 7.

In addition, the average air aperture of measurement porous substrate, result is about 0.1 μm.In the present invention, by with porous substrate Based on electron microscope (SEM) image on surface, the longest distance of stomata is measured to carry out the measurement in average air aperture.The survey The multiplying power of electron microscope (SEM) image used in fixed is 20000 times, and obtained whole stomata diameters are arranged by size order Column, are averaged above 15 numerical value peace mean values, 15 numerical value below, and each visual field is added up to take 30 numerical value, calculate 2 The average value in a visual field obtains average air aperture.It surveys in long, uses the long function of the survey of the software of SEM.

(2) cleaning of porous substrate

By obtained porous substrate ultrasonic cleaning 5 minutes in acetone, ultrasonic cleaning 2 minutes in ethanol, then, Ultrasonic cleaning 1 minute in ion exchange water.

(3) production of aqueous solution of raw material

As raw material, prepare magnesium nitrate hexahydrate (Mg (NO out₃)₂·6H₂O, Kanto Kagaku K. K.'s system), nitric acid Aluminium nonahydrate (Al (NO₃)₃·9H₂O, Kanto Kagaku K. K.'s system) and urea ((NH₂)₂CO, Sigma-Aldrich system). By cation ratio (Mg²⁺/Al³⁺) it is 2 and total metal ion molality (Mg²⁺+Al³⁺) it is 0.320mol/L, weigh magnesium nitrate six Hydrate and aluminum nitrate nonahydrate, and it is put into beaker, ion exchange water is added wherein, makes total amount 75ml.It stirs to get Solution after, will be by urea/NO₃ ^-The urea that=4 ratio weighs is added in solution, futher stirs, it is water-soluble to obtain raw material Liquid.

(4) it is formed a film by hydro-thermal process

The aqueous solution of raw material made in above-mentioned (3) and the porous substrate cleaned in above-mentioned (2) are enclosed into Teflon together In (registered trademark) closed container processed (internal volume 100ml, outside are stainless steel casing).At this point, making substrate from Teflon (note Volume trade mark) bottom of closed container processed floated and fixed, is horizontally disposed in a manner of solution contacted substrate two sides.Then, pass through Implement 168 hours (7 days) hydro-thermal process at 70 DEG C of hydrothermal temperature, forms layered double-hydroxide alignment films in substrate surface (carrier ring).After the stipulated time, substrate is taken out from closed container, is cleaned with ion exchange water, at 70 DEG C dry 10 Hour, the dense film (hereinafter referred to as film sample) of layered double-hydroxide (hereinafter referred to as LDH) is obtained on substrate.Obtained film Sample with a thickness of about 1.5 μm.Thus composite sample (the hereinafter referred to as composite wood containing layered double-hydroxide is obtained Expect sample).It should be noted that LDH film is formed in the two sides of porous substrate, still, in order to have composite material as partition Form carries out mechanical grinding to the LDH film of the one side of porous substrate.

(5) various evaluations

The identification of (5a) film sample

Using X-ray diffraction device (corporation RINT TTR III of science), in voltage: 50kV, current value: 300mA, survey Determine range: under 10~70 ° of determination condition, the crystalline phase of film sample being measured, obtains XRD spectrum shown in Fig. 8.For Obtained XRD spectrum uses the layered double-hydroxide (hydrotalcite-based compound) recorded in JCPDS Card NO.35-0964 Diffraction maximum identified.As a result, it is thus identified that film sample is layered double-hydroxide (LDH, hydrotalcite-based compound).It should say It is bright, in XRD spectrum shown in Fig. 8, also observe together derived from the aluminium oxide for constituting the porous substrate for being formed with film sample Peak (peak that band zero marks in figure).

The observation of (5b) micro-structure

Using scanning electron microscope (SEM, JSM-6610LV, JEOL corporation), with the acceleration voltage of 10~20kV, The surface micro-structure of film sample is observed.The SEM image (secondary electron image) of the surface micro-structure of obtained film sample shows In Fig. 9.

In addition, grinding section is formed come the section of grinding composite material sample by CP grinding, it is aobvious using scanning electron Micro mirror (SEM), the micro-structure that the grinding section is observed with the acceleration voltage of 10~20kV.The composite sample obtained in this way The SEM image of grinding section micro-structure is shown in Figure 10.

The measurement of (5c) porosity

The porosity of film surface is measured by using the method for image procossing for film sample.The measurement of the porosity is such as Lower progress: 1) scanning electron microscope (SEM, JSM-6610LV, JEOL corporation) is used, with the acceleration voltage of 10~20kV Surface micro-structure is observed, obtains electron microscope (SEM) image (10000 times of multiplying power or more) on the surface of film, 2) it uses The image analysis softwares such as Photoshop (Adobe corporation), read the SEM image of tonal gradation, and 3) press [image] → [tone Amendment] → sequentially built the black and white of [binaryzation] bianry image, 4) by pixel number shared by black portions divided by the total of image The resulting value of pixel number is used as the porosity (%).Implement the measurement of the porosity to the region of 6 μm of 6 μ m of alignment layer surface. As a result, the porosity on the surface of film is 19.0%.In addition, using the porosity of the film surface, according to D=100%- (film surface The porosity) calculate from film surface when density D (hereinafter referred to as surface film density), result 81.0%.

In addition, also the porosity in section is ground in measurement for film sample.The measurement of the porosity in the grinding section, in addition to By sequence shown in above-mentioned (5b), electron microscope (SEM) image (multiplying power in the section abradant surface of the thickness direction of film is obtained 10000 times or more) outside, it is carried out similarly with the porosity of above-mentioned film surface.The stomata is implemented to the membrane part in alignment films section Rate measurement.(3 section abradant surfaces are averaged the porosity average out to 3.5% calculated like this by the section abradant surface of film sample Value), it is thus identified that although on porous substrate, foring the very high film of density.

(5d) densification sex determination test

In order to confirm that film sample has the compactness for not having water penetration degree, fine and close sex determination has been carried out as described below Test.Firstly, as shown in Figure 11 A, the film of the composite sample 120 obtained in above-mentioned (1) (being cut into 1cm × 1cm square) Sample side, being bonded in center has the silicon rubber 122 of opening portion 122a of 0.5cm × 0.5cm square, by obtained sandwich with 2 A acrylic container 124,126 is clamped and is engaged.The acrylic container 124 configured in 122 side of silicon rubber is bottomless, thus silicon Rubber 122 is engaged with the open state of its opening portion 122a with acrylic container 124.On the other hand, configuration is in composite material The acrylic container 126 of the porous substrate side of sample 120 has bottom, and ion exchange water 128 is injected in the container 126.At this point, Al and/or Mg can also be made to be dissolved in ion exchange water.That is, being configured to each component parts by running up and down after assembling , ion exchange water 128 is made to contact the porous substrate side of composite sample 120.After the assembling such as these component parts, measurement Total weight.It should be noted that being formed with the venthole (not illustrating) of closing certainly on container 126, it is turned on after turning upside down. As shown in Figure 11 B, assembly is turned upside down and is configured, after 25 DEG C are kept for 1 week, measure total weight again.At this point, in Asia In the case that the inner side surface of gram force container 124 has water droplet, the water droplet is wiped.Then, the total weight of test front and back is calculated Thus difference determines consistency.As a result, even if the weight that ion exchange water is also not observed becomes after 25 DEG C are kept for 1 week Change.Thereby confirm that film sample (i.e. functional membrane) has the high compactness for the degree for not having water penetration.

Example 2: the production and evaluation of nickel-zinc cell

(1) it is accompanied with the preparation of the partition of porous substrate

Prepare hydrotalcite film on aluminum oxide base material as the partition for being accompanied with porous substrate by sequence same as example 1 (size: 5cm × 8cm).

(2) production of positive plate

Prepare the nickel hydroxide particle that zinc and cobalt are added in a manner of becoming solid solution.By the nickel hydroxide particle hydrogen Cobalt oxide is coating to obtain positive active material.2% aqueous solution of obtained positive active material and carboxymethyl cellulose is mixed It closes and prepares paste.It is 50% by the porosity rate of positive active material, is formed by the metal porous substrate of nickel of porosity rate about 95% Collector on be equably coated with paste obtained above, be dried, obtain being coated with active material in the region of 5cm × 5cm Partial positive plate.At this point, adjustment coating weight, makes the nickel hydroxide particle in active material comprising being equivalent to 4Ah.

(3) production of negative plate

On the collector formed by copper punch metal, coating includes 80 parts by weight of Zinc oxide powder, 20 weight of zinc powder The mixture of part and 3 parts by weight of polytetrafluoroethylparticle particle, obtains being coated with about 50% porosity rate, in the region of 5cm × 5cm The negative plate of active substance part.At this point, adjustment coating weight, makes the oxygen in active material comprising being equivalent to positive plate capacity 4Ah Change zinc powder.

(4) assembly of battery

Using positive plate obtained above, negative plate and the partition for being accompanied with porous substrate, filled by sequence as shown below With nickel-zinc cell shown in FIG. 1.

Firstly, preparation removes the ABS resin cuboid housing main body of outer casing upper cover.Near the center of the housing main body Insertion is accompanied with the partition (hydrotalcite film on aluminum oxide base material) of porous substrate and so that porous substrate is located at cathode chamber side and make Partition is located at anode chamber side, its 3 side is fixed on to the inner wall of housing main body using commercially available adhesive.By positive plate and negative plate It is inserted into cathode chamber and anode chamber respectively.At this point, the direction contacted with positive electrode collector and negative electrode collector with housing main body inner wall Configure positive plate and negative plate.To sufficiently flood the KOH aqueous solution of the 6mol/L of the amount of positive active material coated portion as Electrolyte injects in cathode chamber.On the other hand, it not only will sufficiently flood negative electrode active material coated portion but also consider and estimate In charging, the KOH aqueous solution of the 6mol/L of the excess quantity of the amount of moisture of reduction is as in electrolyte injection anode chamber.It will be positive The portion of terminal of collector and negative electrode collector is connect with the external terminal of shell upper respectively.Outer casing upper cover is consolidated by heat bonding It is scheduled on housing main body, by battery case container closure.Thus nickel-zinc cell is obtained.It should be noted that because in the battery, every The size of plate is width 5cm × height 8cm, also, the size of the active material coated portion of positive plate and negative plate is width 5cm × height 5cm, thus the space that the top of cathode chamber and anode chamber is equivalent to 3cm be properly termed as side of the positive electrode remaining space and Negative side remaining space.

(5) it evaluates

To be equivalent to the electric current of the 0.4mA of the 0.1C of design capacitance 4Ah, 10 hours perseverances are implemented to made nickel-zinc cell Current charge.After charging, casing deformation is not observed, electrolyte leaks out.By charging, cathode chamber electrolyte increases, anode chamber Electrolyte is reduced, but has enough electrolyte in negative electrode active material coated portion, can be by coating just by charge and discharge The electrolyte that sufficient discharge and recharge reaction occurs for pole active material and negative electrode active material is kept inside the shell.

Claims

1. a kind of nickel-zinc cell, it includes:

Anode, the anode contain nickel hydroxide and/or hydroxy nickel oxide,

Cathode, the cathode contain zinc and/or zinc oxide,

Closed container, the closed container accommodate the anode, the anode electrolyte, the cathode and the electrolyte Liquid,

Partition, the partition have hydroxide ion conductibility but do not have water penetration, be arranged in the closed container The cathode chamber of the anode and the anode electrolyte will be accommodated and accommodate the anode chamber of the cathode and the electrolyte liquid Zoning is opened,

Porous substrate is provided with the partition in the porous substrate,

There is side of the positive electrode remaining space in the cathode chamber, when the volume of the side of the positive electrode remaining space allows with charge and discharge The amount of moisture that anode is reacted and generated increases and decreases, also, has negative side remaining space in the anode chamber, and the negative side is remaining The amount of moisture that the volume in space allows negative reaction when adjoint charge and discharge and generates subtracts increasing,

In the case where constructing under last current state of discharging, it is more than the anode estimated with when charging that the side of the positive electrode remaining space, which has, It reacts and the volume of increased amount of moisture, is not pre-charged with the anode electrolyte, also, institute in the side of the positive electrode remaining space Stating negative side remaining space to have is more than to estimate with negative reaction when charging and the volume of the amount of moisture of reduction, in the cathode The electrolyte liquid for estimating reduced amount is pre-filled in the remaining space of side,

In the case where constructing under fully charged state, it is more than the anode estimated with when discharging that the side of the positive electrode remaining space, which has, It reacts and the volume of the amount of moisture of reduction, the anode for estimating reduced amount is pre-filled in the side of the positive electrode remaining space Electrolyte, also, it is more than to estimate with negative reaction when discharging and increased amount of moisture that the negative side remaining space, which has, Volume, the electrolyte liquid is not pre-charged in the negative side remaining space.

2. nickel-zinc cell according to claim 1, wherein described just without filling in the side of the positive electrode remaining space Pole, and/or without filling the cathode in the negative side remaining space.

3. nickel-zinc cell according to claim 1, wherein the partition is longitudinally disposed, has in the top of the cathode chamber There is the side of the positive electrode remaining space, also, there is the negative side remaining space in the top of the anode chamber.

4. nickel-zinc cell according to claim 1, wherein the partition is formed by inorganic solid electrolyte body.

5. nickel-zinc cell according to claim 4, wherein the relative density of the inorganic solid electrolyte body be 90% with On.

6. nickel-zinc cell according to claim 4, wherein the inorganic solid electrolyte body includes the double hydroxides of stratiform Object.

7. nickel-zinc cell according to claim 6, wherein layered double-hydroxide basic composition is general formula: M² ⁺ _1-xM³⁺ _x(OH)₂A^n- _x/n·mH₂O, in formula, M²⁺For the cation of divalent, M³⁺For the cation of trivalent, A^n-For the anion of n valence, n For 1 or more integer, x is that 0.1~0.4, m is arbitrary real number.

8. nickel-zinc cell according to claim 7, wherein in the general formula, M²⁺Include Mg²⁺, M³⁺Include Al³⁺, A^n-Packet Containing OH^-And/or CO₃ ^2-。

9. nickel-zinc cell according to claim 4, wherein the inorganic solid electrolyte body has plate, membranaceous or layer The form of shape.

10. nickel-zinc cell according to claim 9, wherein the inorganic solid electrolyte body is membranaceous or stratiform shape State, membranaceous or stratiform the inorganic solid electrolyte body are formed in the porous substrate.

11. nickel-zinc cell according to claim 4, wherein the inorganic solid electrolyte body by hydro-thermal process by Densification.

12. nickel-zinc cell according to claim 1, wherein the alkali metal hydroxide is potassium hydroxide.

13. nickel-zinc cell according to claim 1, also includes: the positive electrode collector of setting is contacted with the anode, and With the negative electrode collector of cathode contact setting.

14. the nickel-zinc cell according to any one of claim 6~8, wherein layered double-hydroxide is by multiple The aggregates of platy particles is constituted, and the multiple platy particles are to their plate face and the surface square crossing of the porous substrate Or the direction orientation obliquely intersected.